Photochromic spiro(indoline)naphthoxazines

ABSTRACT

A photochromic compound for incorporation into plastic articles, particularly into a plastic lens, is selected from a spiro(indoline)naphtho(2,1-b) (1,4)oxazine and a spiro(indoline)naphtho(1,2-b) (1,4)oxazine containing a group selected from: (a) —CH2—CnF2n+1 at the nitrogen atom in the 1-position on the indoline part of the molecule, wherein n is an integer of 1 to 6; (b) —COOR at the 3-position on the indoline part of the molecule, wherein R is (i) C1-C6 alkyl optionally substituted by fluoro, C1-C4 alkoxy or fluoroalkoxy, C1-C4 alkylcarbonyloxy, C2-C4 alkenylcarbonyloxy, C3-C6 cycloalkyl or aryl; (ii) C2-C6 alkenyl with a terminal double bond; (iii) C3-C6 cycloalkyl optionally substituted by fluoro; or (iv) aryl; (c) an —OCF3 group on the benzene ring of the indoline part of the molecule; (d) an aryl(dialkyl)methyl group of the formula —C(aryl) (CnH2n+1) (CmH2m+1), wherein n and m are integers from 1 to 5, linked to one of the benzene rings of the naphthoxazine part of the molecule; and (e) any combination of (a), (b), (c) and/or (d).

FIELD OF THE INVENTION

[0001] The present invention relates to certain novel photochromicspiro(indolino)naphthoxazine compounds and to articles comprising them.

BACKGROUND OF THE INVENTION

[0002] Spiro(indolino)oxazine compounds have been found to be useful forimparting photochromic properties to a polymeric host material. Examplesof spirooxazine and their use in photochromic lenses have been reviewedby Crano et al. in Applied Photochromic Polymer Systems (C. B. McArdle,Ed.) Blackie & Sons, Glasgow, London, 1992, pp. 31-76. As a rule, theunsubstituted spiroindolinonaphthoxazines give a rather low opticaldensity of the blue color on exposure to light.

[0003] Several U.S. patents describespiro(indoline)naphtho(2,1-b)(1,4)oxazine compounds (see for exampleU.S. Pat. Nos. 4,959,471 (Melzig), 4,913,544, 5,446,149, 5,446,150,5,446,151 (Rickwood et al.), 5,186,867 (Castaldi et al.), 5,405,958 (VanGemert), 5,936,016 (Lareginie et al.), 6,004,486 and 6,030,555 (You-PingChan)) that are said to give enhanced optical density on exposure tosunlight. The enhancement of the photoinduced optical density wasachieved mainly by introducing electron-donor or -acceptor substituentsin the naphthalene moiety of the molecule, while the absorption maximumof the colored form remains in the region of 570-630 nm.

[0004] U.S. Pat. Nos. 4,851,530 and 5,833,885 (Rickwood et al) describespirooxazines showing substantial change in the kinetic and spectralproperties of spirooxazines by modification of the 1-position in theindoline ring with the absorption maxima of the photoactivated formshorter than 570 nm (mainly red). PCT Publication No. WO 99/20630describe photochromic spiro (indoline)naphtho( 1,2-b)(1,4)oxazinecompounds.

[0005] The present invention relates to novelspiro(indoline)naphtho(2,1-b)(1,4)oxazine andspiro(indoline)naphtho(1,2-b)(1,4)oxazine compounds that have particularsubstituents on the indoline and/or on the naphthalene part of themolecule. None of the publications mentioned above describe thecompounds of the present invention.

SUMMARY OF THE INVENTION

[0006] The present invention relates to novel photochromicspiro(indoline)naphtho(2,1-b) (1,4)oxazine andspiro(indoline)naphtho(1,2-b)(1,4)oxazine compounds containing certainparticular groups as follows:

[0007] (a) —CH₂—C_(n)F_(2n+1) at the nitrogen atom in the 1-position onthe indoline part of the molecule, wherein n is an integer of 1 to 6;

[0008] (b) —COOR at the 3-position on the indoline part of the molecule,wherein R is (i) C₁-C₆ alkyl optionally substituted by fluoro, C₁-C₄alkoxy or fluoroalkoxy, C₁-C₄ alkylcarbonyloxy, C₂-C₄alkenylcarbonyloxy, C₃-C₆ cycloalkyl or aryl; (ii) C₂-C₆ alkenyl with aterminal double bond; (iii) C₃-C₆ cycloalkyl optionally substituted byfluoro; or (iv) aryl;

[0009] (c) an —OCF₃ group on the benzene ring of the indoline part ofthe molecule;

[0010] (d) an aryl(dialkyl)methyl group of the formula—C(aryl)(C_(n)H_(2n+1))(C_(m)H_(2m+1)), wherein n and m are integersfrom 1 to 5, linked to one of the benzene rings of the naphthoxazinepart of the molecule; and

[0011] (e) any combination of (a), (b), (c) and/or (d).

[0012] The photochromic compounds of the present invention provide asubstantial increase of the photoactivation and decoloration rates whileretaining a high optical density in the photoactivated state.Incorporation of these compounds into a plastic lens or another plasticarticle provides the articles with desirable photochromic properties.

DETAILED DESCRIPTION OF THE INVENTION

[0013] In one preferred embodiment of the present invention, thespiro(indoline)naphtho(2,1-b)(1,4)oxazine andspiro(indoline)naphtho(1,2-b)(1,4) oxazine compounds have at thenitrogen atom in the 1-position on the indoline part of the molecule aradical —CH₂—C_(n)F_(2n+1), and have the formulas Ia and Ib,respectively:

[0014] wherein

[0015] (a) n is an integer from 1 to 6; p is 1 or 2; and q is an integerfrom 1 to 6;

[0016] (b) R₂ and R₃ represent independently a radical selected from:(i) C₁-C₆ alkyl optionally substituted by fluoro, C₁-C₄ alkoxy orfluoroalkoxy, C₁-C₄ alkylcarbonyloxy, C₂-C₄ alkenylcarbonyloxy, C₃-C₆cycloalkyl or aryl-; (ii) C₂-C₆ alkenyl with a terminal double bond;(iii) C₃-C₆ cycloalkyl optionally substituted by fluoro; (iv) aryl; (v)alkylcarbonyl; or (vi) one of R₂ and R₃ is a group —COOR wherein R is aradical (i) to (iv) as defined hereinbefore and the other of R₂ and R₃is a radical (i) to (iv) as defined hereinbefore; or (vii) R₂ and R₃together with the carbon atom at position 3 of the indoline ring form a3-7 membered saturated ring optionally containing a heteroatom selectedfrom nitrogen, oxygen or sulfur, and

[0017] (c) R₄ and R₅ represent independently (i) hydrogen; (ii) halogen,preferably fluoro; or a radical selected from: (iii) cyano; (iv) aryloxyoptionally substituted by C₁-C₆ alkyl, C₁-C₄ alkoxy or amino; (v) C₁-C₄alkoxy optionally substituted by halogen, preferably di- andtrifluoromethoxy; (vii) C₁-C₆ alkyl optionally substituted by C₁-C₄alkoxy, halogen, preferably trifluoromethyl, C₃-C₆ cycloalkyl,polycycloalkyl (such as norbomane or adamantane), aryl or heterocyclyl;(viii) aryl optionally substituted with amino or alkoxy group,preferably dialkylaminophenyl or methoxyphenyl; (ix) amide (—CONH₂); (x)sulfonamide (—SO₂NH₂); (xi) —NR₆R₇, wherein R₆ and R₇ are independentlyselected from alkyl, alkenyl, cycloalkyl, aryl, alkylaryl, fluoroalkyl(preferably trifluoromethyl) or R₆ and R₇ together with the nitrogenatom form a 3-7 membered saturated ring optionally containing a furtherheteroatom selected from nitrogen, oxygen or sulfur atom, preferablypiperidino, piperazino or morpholino; (xii) R₄ may further be —OCF₃, inwhich case p is 1; and (xiii) R₅ may further be an aryl(dialkyl)methylgroup of the formula —C(aryl)(C_(n)H_(2n+1))(C_(m)H_(2m+1)), wherein nand m are integers from 1 to 5, linked to one of the benzene rings ofthe naphthoxazine part of the molecule, in which case q is an integerfrom 1 to 5.

[0018] In another preferred embodiment of the present invention, thespiro(indoline)naphtho(2,1-b)(1,4)oxazine andspiro(indoline)naphtho(1,2-b)(1,4) oxazine compounds have at the3-position on the indoline part of the molecule a group —COOR, wherein Ris selected from: (i) C₁-C₆ alkyl optionally substituted by fluoro,C₁-C₄ alkoxy or fluoroalkoxy, C₁-C₄ alkylcarbonyloxy, C₂-C₄alkenylcarbonyloxy, C₃-C₆ cycloalkyl or aryl; (ii) C₂-C₆ alkenyl with aterminal double bond; (iii) C₃-C₆ cycloalkyl optionally substituted byfluoro; or (iv) aryl; and have the formulas IIa and IIb, respectively:

[0019] wherein

[0020] (a) p is 1 or 2 and q is an integer from 1 to 6;

[0021] (b) R₁ is a radical selected from: (i) C₁-C₆ alkyl optionallysubstituted by C₁-C₄ alkoxy, C₁-C₄ alkylcarbonyloxy, C₂-C₄alkenylcarbonyloxy, C₃-C₆ cycloalkyl, polycycloalkyl, aryl orheterocyclic ring; (ii) C₃-C₆ cycloalkyl; (iii) polycycloalkyl: (iv)aryl; (v) heterocyclic ring; (vi) —CH₂—C_(n)F_(2n+1) wherein n is aninteger of 1 to 6; or (vii) C₂-C₆ alkenyl with a terminal double bond;

[0022] (c) R₃ represents a radical selected from: (i) C₁-C₆ alkyloptionally substituted by fluoro, C₁-C₄ alkoxy or fluoroalkoxy, C₁-C₄alkylcarbonyloxy, C₂-C₄ alkenylcarbonyloxy, C₃-C₆ cycloalkyl or aryl;(ii) C₂-C₆ alkenyl with a terminal double bond; (iii) C₃-C₆ cycloalkyloptionally substituted by fluoro ; or (iv) aryl; and

[0023] (d) R₄ and R₅ represent independently (i) hydrogen; (ii) halogen,preferably fluoro; or a radical selected from: (iii) cyano; (iv) aryloxyoptionally substituted by C₁-C₆ alkyl, C₁-C₄ alkoxy or amino; (v) C₁-C₄alkoxy optionally substituted by halogen, preferably di- andtrifluoromethoxy; (vii) C₁-C₆ alkyl optionally substituted by C₁-C₄alkoxy, halogen, preferably trifluoromethyl, C₃-C₆ cycloalkyl,polycycloalkyl (such as norbomane or adamantane), aryl or heterocyclyl;(viii) aryl optionally substituted with amino or alkoxy group,preferably dialkylaminophenyl or methoxyphenyl; (ix) amide (—CONH₂); (x)sulfonamide (—SO₂NH₂); (xi) —NR₆R₇, wherein R₆ and R₇ are independentlyselected from alkyl, alkenyl, cycloalkyl, aryl, alkylaryl, fluoroalkyl(preferably trifluoromethyl) or R₆ and R₇ together with the nitrogenatom form a 3-7 membered saturated ring optionally containing a furtherheteroatom selected from nitrogen, oxygen or sulfur atom, preferablypiperidino, piperazino or morpholino; (xii) R₄ may further be —OCF₃, inwhich case p is 1; and (xiii) R₅ may further be an aryl(dialkyl)methylgroup of the formula —C(aryl)(C_(n)H_(2n+1))(C_(m)H_(2m+1)), wherein nand m are integers from 1 to 5, linked to one of the benzene rings ofthe naphthoxazine part of the molecule, in which case q is an integerfrom 1 to 5.

[0024] In a further preferred embodiment of the present invention, thespiro(indoline)naphtho(2,1-b)(1,4)oxazine andspiro(indoline)naphtho(1,2-b)(1,4) oxazine compounds have atrifluoromethoxy (—OCF₃) group on the benzene ring of the indoline partof the molecule, and have the formulas IIIa and IIIb, respectively:

[0025] wherein

[0026] (a) q is an integer from 1 to 6;

[0027] (b) R₁ is a radical selected from: (i) C₁-C₆ alkyl optionallysubstituted by C₁-C₄ alkoxy, C₁-C₄ alkylcarbonyloxy. C₂-C₄alkenylcarbonyloxy, C₃-C₆ cycloalkyl, polycycloalkyl, aryl orheterocyclic ring; (ii) C₃-C₆ cycloalkyl; (iii) polycycloalkyl: (iv)aryl; (v) heterocyclic ring; (vi) —CH₂-C_(n)F_(2n+1) wherein n is aninteger of 1 to 6; or (vii) C₂-C₆ alkenyl with a terminal double bond;

[0028] (c) R₂ and R₃ represent independently a radical selected from:(i) C₁-C₆ alkyl optionally substituted by fluoro, C₁-C₄ alkoxy orfluoroalkoxy, C₁-C₄ alkylcarbonyloxy, C₂-C₄ alkenylcarbonyloxy, C₃-C₆cycloalkyl or aryl; (ii) C₂-C₆ alkenyl with a terminal double bond;(iii) C₃-C₆ cycloalkyl optionally substituted by fluoro; (iv) aryl; or(v) alkylcarbonyl; or (vi) one of R₂ and R₃ is a group —COOR wherein Ris a radical (i) to (iv) as defined hereinbefore and the other of R₂ andR₃ is a radical (i) to (iv) as defined hereinbefore; or (vii) R₂ and R₃together with the carbon atom at position 3 of the indoline ring form a3-7 membered saturated ring optionally containing a heteroatom selectedfrom nitrogen, oxygen or sulfur, and

[0029] (d) R₄ and R₅ represent independently (i) hydrogen; (ii) halogen,preferably fluoro; or a radical selected from: (iii) cyano; (iv) aryloxyoptionally substituted by C₁-C₆ alkyl, C₁-C₄ alkoxy or amino; (v) C₁-C₄alkoxy optionally substituted by halogen, preferably di- andtrifluoromethoxy; (vii) C₁-C₆ alkyl optionally substituted by C₁-C₄alkoxy, halogen, preferably trifluoromethyl, C₃-C₆ cycloalkyl,polycycloalkyl (such as norbornane or adamantane), aryl or heterocyclyl;(viii) aryl optionally substituted with amino or alkoxy group,preferably dialkylaminophenyl or methoxyphenyl; (ix) amide (—CONH₂); (x)sulfonamide (—SO₂NH₂); (xi) —NR₆R₇, wherein R₆ and R₇ are independentlyselected from alkyl, alkenyl, cycloalkyl, aryl, alkylaryl, fluoroalkyl(preferably trifluoromethyl) or R₆ and R₇ together with the nitrogenatom form a 3-7 membered saturated ring optionally containing a furtherheteroatom selected from nitrogen, oxygen or sulfur atom, preferablypiperidino, piperazino or morpholino; and (xii) R₅ may further be anaryl(dialkyl)methyl group of the formula—C(aryl)(C_(n)H_(2n+1))(C_(m)H_(2m+1)), wherein n and m are integersfrom 1 to 5, linked to one of the benzene rings of the naphthoxazinepart of the molecule, in which case q is an integer from 1 to 5.

[0030] In still a further preferred embodiment of the present invention,the spiro(indoline)naphtho(2,1-b)(1,4)oxazine andspiro(indoline)naphtho(1,2-b)(1,4) oxazine compounds have anaryl(dialkyl)methyl group of the formula—C(aryl)(C_(n)H_(2n+1))(C_(m)H_(2m+1)), wherein n and m are integersfrom 1 to 5, linked to one of the benzene rings of the naphthoxazinepart of the molecule, and have the formulas IVa and IVb, respectively:

[0031] wherein

[0032] (a) p is 1 or 2 and q is an integer from 1 to 5;

[0033] (b) R₁ is a radical selected from: (i) C₁-C₆ alkyl optionallysubstituted by C₁-C₄ alkoxy, C₁-C₄ alkylcarbonyloxy, C₂-C₄alkenylcarbonyloxy, C₃-C₆ cycloalkyl, polycycloalkyl, aryl orheterocyclic ring; (ii) C₃-C₆ cycloalkyl; (iii) polycycloalkyl: (iv)aryl; (v) heterocyclic ring; (vi) —CH₂—C_(n)F_(2n+1) wherein n is aninteger of 1 to 6; or (vii) C₂-C₆ alkenyl with a terminal double bond;

[0034] (c) R₂ and R₃ represent independently a radical selected from:(i) C₁-C₆ alkyl optionally substituted by fluoro, C₁-C₄ alkoxy orfluoroalkoxy, C₁-C₄ alkylcarbonyloxy, C₂-C₄ alkenylcarbonyloxy, C₃-C₆cycloalkyl or aryl; (ii) C₂-C₆ alkenyl with a terminal double bond;(iii) C₃-C₆ cycloalkyl optionally substituted by fluoro; (iv) aryl; or(v) alkylcarbonyl; or (vi) one of R₂ and R₃ is a group —COOR wherein Ris a radical (i) to (iv) as defined hereinbefore and the other of R₂ andR₃ is a radical (i) to (iv) as defined hereinbefore; or (vii) R₂ and R₃together with the carbon atom at position 3 of the indoline ring form a3-7 membered saturated ring optionally containing a heteroatom selectedfrom nitrogen, oxygen or sulfur, and

[0035] (d) R₄ and R₅ represent independently (i) hydrogen; (ii) halogen,preferably fluoro; or a radical selected from: (iii) cyano; (iv) aryloxyoptionally substituted by C₁-C₆ alkyl, C₁-C₄ alkoxy or amino; (v) C₁-C₄alkoxy optionally substituted by halogen, preferably di- andtrifluoromethoxy; (vii) C₁-C₆ alkyl optionally substituted by C₁-C₄alkoxy, halogen, preferably trifluoromethyl, C₃-C₆ cycloalkyl,polycycloalkyl (such as norbomane or adamantane), aryl or heterocyclyl;(viii) aryl optionally substituted with amino or alkoxy group,preferably dialkylaminophenyl or methoxyphenyl; (ix) amide (—CONH₂); (x)sulfonamide (—SO₂NH₂); (xi) —NR₆R₇, )wherein R₆ and R₇ are independentlyselected from alkyl, alkenyl, cycloalkyl, aryl, alkylaryl, fluoroalkyl(preferably trifluoromethyl) or R₆ and R₇ together with the nitrogenatom form a 3-7 membered saturated ring optionally containing a furtherheteroatom selected from nitrogen, oxygen or sulfur atom, preferablypiperidino, piperazino or morpholino; and (xii) R₄ may further be —OCF₃,in which case p is 1.

[0036] According to the invention, the alkyl and alkoxy radicals may belinear or branched. The C₂-C₄ alkenylcarbonyloxy radical is preferablythe radical derived from acrylic (—O—CO—CH═CH₂) or methacrylic(—O—CO—C(CH₃)═CH₂) acid. The C₃-C₆ cycloalkyl is preferably cyclopentylor cyclohexyl and the polycycloalkyl may be a C₄-C₂₀ bicycloalkyl suchas partially or completely saturated naphthyl or a C₆-C₂₀ tricycloalkylsuch as adamantyl and norbornyl. The C₂-C₆ alkenyl with a terminaldouble bond is preferably —CH₂—CH═CH₂ or —CH₂—(CH₂)₃—CH═CH₂. Thepreferred radicals —CH₂—C_(n)F_(2n+1) are —CH₂—CF₃ and —CH₂—CF₂—CF₃. TheC₁-C₄ fluoroalkoxy radical is preferably —OCF₃. When R₅ is anaryl(dialkyl)methyl group of the formula—C(aryl)(C_(n)H_(2n+1))(C_(m)H_(2m+1)), n and m are preferably 1 suchthat said linking group is preferably tert-propylene (CH₃)—C—(CH₃).

[0037] Further, the present invention provides synthetic methods formaking the photochromic spirooxazine molecules of the invention. Thecompounds containing a COOR group on the 3-position of the indoline ringare prepared by the reaction of a Fischer base containing theaforementioned carboxylic ester structure at 3-position with thesuitable 1-nitroso-2-naphthol non-substituted or substituted with one ormore R₅ groups. The compounds containing a F₃CO— group on the benzenering of the indoline molecule are prepared by the reaction of a Fischerbase containing the aforementioned trifluoromethoxy group on the benzenering with the suitable 1-nitroso-2-naphthol non-substituted orsubstituted with one or more R₅ groups. The compounds containing a—CH₂—C_(n)F_(2n+1) group at the 1-position of the indoline ring areprepared by the reaction of a Fischer base containing the aforementionedpolyfluoroalkyl group at the 1-position with the suitable1-nitroso-2-naphthol non-substituted or substituted with one or more R₅groups. The compounds wherein R₅ is an aryl(dialkyl)methyl group of theformula —C(aryl)(C_(n)H_(2n+1))(C_(m)H_(2m+1)), wherein n and m areintegers from 1 to 5, linked to one of the benzene rings of thenaphthoxazine part of the molecule, can be prepared by reaction betweennaphthol substituted with aryl(dialkyl)methyl group and the suitableFisher base.

[0038] The photochromic compounds of the present invention and mixturesthereof and/or their mixtures with other photochromic compounds known inthe art may be incorporated into a plastic lens, car window or otherarticles, giving high optical density of color on irradiation withsunlight. The aforementioned photochromic compounds or their mixturescan be incorporated into a plastic object, preferably a plastic lens, byany conventional method known in the art, for example, by moldingtechniques, e.g., injection molding, press-molding or by polymerizationtechniques, e.g., by thermal polymerization of a photochrome solution ina polymerizable monomer containing a catalyst, for example,azo-isobutyronytryl, giving free radicals on heating.Micro-encapsulation techniques can also be employed. A photochromiccompound may be incorporated in a polymer host also by thermodiffusionthrough the lens surface. A mixture of different photochromes can beincorporated into a plastic object.

[0039] The present invention, thus, further relates to a photochromicarticle comprising a plastic object containing a photochromic compoundof the present invention or mixtures thereof with a photochrome known inthe art such as, but not being limited to, spirooxazines, naphthopyransand fulgides. The article may also contain additives such asplasticizers, materials for the photochrome microencapsulation and lightstabilizers such as hindered amines or phenols. The photochromic articleis preferably a plastic lens.

[0040] The invention will now be illustrated by the following examples,to which it is not limited.

EXAMPLES Example 1

[0041] Preparation of1,3,3-Trimethyl-5-Trifluoromethoxy-Spiro-(Indoline-2,3′-(3H)-Naphtho[2,1-b]-(1,4)-Oxazine)

[0042] A solution of 1-nitroso-2-naphthol (0.50 g, 2.89 mmol) and1,3,3-trimethyl-5-trifluoromethoxy-2-methylene-indoline (0.71 g, 2.77mmol) in ethanol (30 ml) was heated under nitrogen and refluxed for 20hrs. The solvent was then evaporated and the residue was chromatographedover silica (ethyl acetate/petroleum ether 1:10). After crystallizationin ethanol, the yield of the pure product (colorless crystals) was 0.2 g(18%).

[0043] In the photoactivated colored form in the polystyrene film, thephotochrome has a broad absorption band with maximum at 580 nm.

[0044] The compounds listed below as Examples 2-4 were prepared by asynthetic procedure analogous to that described in Example 1.

Example 2

[0045]1-Cyclohexylmethyl-3,3-Dimethyl-5-Trifluoromethoxy-6′-Dimethylamino-Spiro-(Indoline-2,3′-(3H)-Naphtho[2,1-b]-(1,4)-Oxazine)

[0046] This compound presented an absorption band with λ_(max) 555 nm inthe photoactivated form.

Example 3

[0047]1-Propyl-3,3-Dimethyl-5-Trifluoromethoxy-6′-Dimethylamino-Spiro-(Indoline-2,3′-(3H)-Naphtho[2,1-b]-(1,4)-Oxazine)

[0048] This compound presented an absorption band with λ_(max) 550 nm inthe photoactivated form.

Example 4

[0049]1-Propyl-3,3-Dimethyl-5-Trifluoromethoxy-6′-Piperidino-Spiro-(Indoline-2,3′-(3H)-Naphtho-[2,1-b]-(1,4)-Oxazine)

[0050] This compound presented an absorption band with λ_(max) 558 nm inthe photoactivated form.

Example 5 (Comparative)

[0051] The spirooxazines described in examples 1-4 and two knownspirooxazines depicted by the formulas below were individuallyincorporated (5%) in a polystyrene film of 5 μm.

[0052] The results of the photochromic property examinations of thecompounds are presented in Table 1, where OD is the optical density ofthe film at the photoinduced color absorption maximum (λ_(max)), τ_(1/2)is the halftime of color fading in the dark, and activation time is whenthe film reaches a steady-state color on irradiation with UV-light of a250 W mercury lamp.

[0053] Table 1 shows that substitution in the phenyl ring of theindoline moiety with a trifluoromethoxy group brings about a profoundhypsochromic shift, acceleration in the color decay and photoactivationprocesses.

Example 6

[0054] Preparation of1,3-Dimethyl-3-Carboethoxy-Spiro-(Indoline-2,3′-(3H)-Naphtho[2,1-b]-(1,4)-Oxazine)

[0055] A solution of 1-nitroso-2-naphthol (0.50 g, 2.89 mmol) and1,3-dimethyl-3-carboethoxy-2-methylene-indoline (0.87 g, 2.77 mmol) inethanol (70 ml) was heated under nitrogen and refluxed for 2 hrs. Thesolvent was then evaporated and the residue was chromatographed oversilica (ethyl acetate/petroleum ether 1:10). After crystallization inethanol, the yield of the pure product (colorless crystals) was 0.21 g(16%).

[0056] In the photoactivated colored form in the polystyrene film, thephotochrome has a broad absorption band with a maximum at 596 nm and ashoulder at 568 nm.

[0057] The compounds listed below as Examples 7-20 were prepared by asynthetic procedure analogous to that described in Example 6.

Example 7

[0058]1-Cyclohexylmethyl-3-Methyl-3-Carboethoxy-Spiro-(Indoline-2,3′-(3H)-Naphtho[2,1-b]-(1,4)-Oxazine)

[0059] This compound presented a broad absorption band with λ_(max) 602nm and a shoulder at 568 nm in the photoactivated form.

Example 8

[0060]1,3,4,5-Tetramethyl-3-Carboethoxy-Spiro-(Indoline-2,3′-(3H)-Naphtho[2,1-b]-(1,4)-Oxazine).

[0061] This compound presented a broad absorption band with λ_(max) 612nm and a shoulder at 574 nm in the photoactivated form.

Example 9

[0062]1,3,4,5-Tetramethyl-3-Carboethoxy-8′-(1-Methyl-1-Phenyl)Ethyl-Spiro-(Indoline-2,3′-(3H)-Naphtho[2,1-b]-(1,4)-Oxazine)

[0063] This compound presented a broad absorption band with λ_(max) 580,614 nm in the photoactivated form.

Example 10

[0064]1,3-Dimethyl-3-Carboethoxy-9′-Acetyloxy-Spiro-(Indoline-2,3′-(3H)-Naphtho-[2,1-b]-(1,4)-Oxazine).

[0065] This compound presented a broad absorption band with λ_(max) 575593 nm in the photoactivated form.

Example 11

[0066]1-Isobutyl-3-Methyl-3-Carboethoxy-Spiro-(Indoline-2,3′-(3H)-Naphtho[2,1-b]-(1,4)-Oxazine).

[0067] This compound presented a broad absorption band with λ_(max) 570,600 nm in the photoactivated form.

Example 12

[0068]1-Isobutyl-3,5-Dimethyl-3-Carboethoxy-Spiro-(Indoline-2,3′-(3H)-Naphtho[2,1-b]-(1,4)-Oxazine).

[0069] This compound presented a broad absorption band with λ_(max) 580,605 nm in the photoactivated form.

Example 13

[0070]1,3-Dimethyl-3-Carboethoxy-8′-(1-Methyl-1-Phenyl)-Ethyl-Spiro-(Indoline-2,3′-(3H)-Naphtho-[2,1-b]-(1,4)-Oxazine)

[0071] This compound presented a broad absorption band with λ_(max) 577,599 nm in the photoactivated form.

Example 14

[0072]1,3,5,6-Tetramethyl-3-Carboethoxy-Spiro-(Indoline-2,3′-(3H)-Naphtho-[2,1-b]-(1,4)-Oxazine)

[0073] This compound presented a broad absorption band with λ_(max) 567,606 nm in the photoactivated form.

Example 15

[0074]1-Cyclohexylmethyl-3-Methyl-3-Carboethoxy-6′-Dimethylamino-Spiro-(Indoline-2,3′-(3H)-Naphtho-[2,1-b]-(1,4)-Oxazine)

[0075] This compound presented a maximum absorption band with λ_(max)575 nm in the photoactivated form.

Example 16

[0076]1-Propyl-3,5-Dimethyl-3-Carboethoxy-Spiro-(Indoline-2,3′-(3H)-Naphtho-[2,1-b]-(1,4)-Oxazine)

[0077] This compound presented a maximum absorption band with λ_(max)578, 603 nm in the photoactivated form.

Example 17

[0078]1,3-Dimethyl-3-Carboethoxy-6′-Methoxy-Spiro-(Indoline-2,3′-(3H)-Naphtho-[2,1-b]-(1,4)-Oxazine)

[0079] This compound presented a maximum absorption band with λ_(max)552 nm in the photoactivated form.

Example 18

[0080]1-(2-Phenylethyl)-3-Methyl-3-Carboethoxy-Spiro-(Indoline-2,3′-(3H)-Naphtho-[2,1-b]-(1,4)-Oxazine)

[0081] This compound presented a maximum absorption band with λ_(max)600 nm in the photoactivated form.

Example 19

[0082]1-Ethyl-3,5-dimethyl-3-Carboethoxy-Spiro-(Indoline-2,3′-(3H)-Naphtho-[2,1-b]-(1,4)-Oxazine)

[0083] This compound presented a maximum absorption band with λ_(max)600 nm in the photoactivated form.

Example 20

[0084]1-Isobutyl-5-Fluoro-3-Methyl-3-Carboethoxy-Spiro-(Indoline-2,3′-(3H)-Naphtho-[2,1-b]-(1,4)-Oxazine)

[0085] This compound presented a maximum absorption band with λ_(max)595 nm in the photoactivated form.

Example 21

[0086] For comparison, the spirooxazines described in examples 6-9above, the new spirooxazine (iii) below and the known spirooxazinesdepicted by Formulas (i) and (ii) below were individually incorporated(5%) in a polystyrene film of 5 μm.

[0087] The results of the photochromic property examination of thecompounds are shown in Table 2, wherein OD is the optical density of thefilm at the photoinduced color absorption maximum (λ_(max)), τ_(1/2) isthe halftime of color fading in the dark, and activation time is whenthe film reaches a steady-state color on irradiation with UV-light of a250 W mercury lamp. Table 2 shows that substitution of the indoline ringin the 3-position with a carboalkoxy group brings about a profoundenhancement in optical density. Examination of the spirooxazinemolecular models indicates that this effect may be ascribed tointeraction between the carbonyl oxygen and the proton at 2′-position.

Example 22

[0088] Preparation of 1-(2,2,2-Trifluoroethyl)-3,3-Dimethyl-6′(4-DiethylAminophenyl)-Spiro-(Indoline-2,3′-(3H)-Naphtho[2,1-b]-(1,4)-Oxazine)

[0089] The title compound of formula I′a below was prepared by thefollowing steps:

[0090] 22a. Preparation of 1-Phenyl-1-(2,2,2-Trifluoroethyl)Hydrazine,Hydrochloric Salt

[0091] Ten ml of 10% HCl was added to a solution of 2,2,2-trifluoroethylaniline (1.07 g, 0.0061 mol) in 30 ml dichloromethane. The solution wascooled to 5-7° C. and then a solution of 0.6 g (0.0086 mol) NaNO₂ in 2ml of water was added. After stirring for 2 hours, the lower layer,containing product (b) in CH₂Cl₂, was separated. The solvent wasevaporated and the residue was dissolved in 20 ml of ethanol. 2 g ofammonium carbonate and 4 g Zn powder were added. The mixture was cooledto 5-6° C. and 4.5 ml of 25% NH₄OH solution were added very slowly withvigorous stirring. Then 2 g of Zn powder was added again and the mixturewas stirred for 10 h.

[0092] On completion of the reaction, excess Zn was separated byfiltration. The filtrate was diluted with 100 ml of water, and theproduct was extracted with ethyl ether. After ether evaporation, 10 mlof 10% HCl were added. The precipitated hydrochloric salt of thehydrazine (c) was separated by filtration and washed on filter withethyl ether (3×10 ml).

[0093] 22b. Preparation of1-(2,2,2-Trifluoroethyl)-3,3-Dimethyl-2-Methylene-Indoline

[0094] A solution of the hydrochloride (c) obtained above (0.135 g) andmethyl isopropyl ketone (0.5 ml) in 10 ml of ethanol was refluxed for 4hours, followed by addition of 0.3 ml of triethylamine for another hour.After separation of the solvent, the residue was dissolved in 20 mlpetroleum ether and stirred for 5 hours with 1 g of activated carbon.Following filtration and evaporation of the solvent, the product (d) wasisolated and used further without additional purification.

[0095] 22c. The final product (I′a) was prepared by reacting the Fisherbase (d) and 1-nitroso-2-hydroxy-4-(p-diethylaminophenyl)naphthalene(e), according to procedures well known in the art.

Example 23

[0096] For comparison, the photochromic compound1-neopentyl-3,3-dimethyl-6′-(p-diethylamino-phenyl)-spiro-(indoline-2,3′-(3H)-naphtho-[2,1-b]-(1,4)-oxazinedescribed in Example 10 of U.S. Pat. No. 5,446,151 was synthesized:

[0097] Table 3 gives a comparison of the main characteristics of thephotochrome I′a of the invention and the photochrome above described inU.S. Pat. No. 5,446,151, in a polystyrene film. TABLE 3 Visual OpticalTime of Decoloration Exam- Density in the Photoactivation to Half-time,ple λ_(max) Photoactivated State Steady State, min. min 22 595 nm 1.3  510 23 622 nm 1.25 40 >70

[0098] The results in Table 3 indicate that compound I′a of theinvention has a substantially better photoresponse and a much higherdecoloration rate than the compound described in U.S. Pat. No.5,446,151, which is considered to be a very efficient photochromic dye(D. Clarke et al., Effects in Plastics, SPE, RETTEC, Chicago, 1995).

Example 24

[0099]1-(2,2,2-Trifluoroethyl)-3,3-Dimethyl-Spiro-(Indoline-2,3′-(3H)-Naphtho-[2,1-b]-(1,4)-Oxazine),

[0100] The compound presented an absorbtion band with λ_(max) 570 nm inthe photoactivated form.

Example 25

[0101] 1-Cyclohexylmethyl-3,3-Spiro-(Cyclohexyl)-8′-(1-Methyl-1-Phenyl)Ethyl-Spiro-(Indoline-2,3′-(3H)-Naphtho-[2,1-b]-(1,4)-Oxazine),

[0102] This compound of formula (iii) in Example 21 presented a maximumabsorption band with λ_(max) 620 nm in the photoactivated form.

Example 26

[0103]1-Cyclohexylmethyl-3,3-Dimethyl-8′-(1-Methyl-1-Phenyl)Ethyl-Spiro-(Indoline-2,3′-(3H)-Naphtho-[2,1-b]-(1,4)-Oxazine),

[0104] This compound presented a broad absorption band with λ_(max) 575,612 nm in the photoactivated form.

Example 27

[0105]1-Cyclohexylmethyl-3,3-Dimethyl-6′-Morpholino-8′-(1-Methyl-1-Phenyl)Ethyl-Spiro-(Indoline-2,3′-(3H)-Naphtho-[2,1-b]-(1,4)-Oxazine),

[0106] The compound presented an absorbtion band with λ_(max) 580 nm inthe photoactivated form.

Example 28

[0107]1-Cyclohexylmethyl-3,3-Dimethyl-6′-Morpholino-8′-(1-Methyl-1-Phenyl)Ethyl-Spiro-(Indoline-2,3′-(3H)-Naphtho-[1,2-b]-(1,4)-Oxazine).

[0108] The compound presented an absorbtion band with λ_(max) 570 nm inthe photoactivated form.

Example 29

[0109]1-Propyl-3,5-Dimethyl-3-Carboethoxy-Spiro-(Indoline-2,3′-(3H)-Naphtho-[1,2-b]-(1,4)-Oxazine)

[0110] This compound presented a maximum absorption band with λ_(max)603 nm in the photoactivated form. TABLE 1 Example λ_(max) OD τ_(1/2)Activation No. R₁ R₂ R₃ R₄ R₅ nm at λ_(max) min time-min 1 CH₃ CH₃ CH₃OCF₃ H 580 0.4 <0.1  3 2 CH₂-(cyclo)C₆H₁₁ CH₃ CH₃ OCF₃ 6′-N(CH₃)₂ 5552.2 5 15 3 C₃H₇ CH₃ CH₃ OCF₃ 6′-N(CH₃)₂ 550 3.0 5 15 4 C₃H₇ CH₃ CH₃ OCF₃(cyclo)C₅H₁₀N 558 2.5 6 10 5 (comp.) CH₃ CH₃ CH₃ H H 598 0.3 0.5 15 5(comp.) CH₂-(cyclo)C₆H₁₁ CH₃ CH₃ H 6′-N(CH₃)₂ 570 2.5 22 30

[0111] TABLE 2 Example λ_(max) OD τ_(1/2) Activation No. R₁ R₂ R₃ R₄ R₅nm at λ_(max) min time-min  6 CH₃ COOC₂H₅ CH₃ H H 568, 596 3.85 3.5 10 7 CH₂-(cyclo)C₆H₁₁ COOC₂H₅ CH₃ H H 568, 602 6.60 18 40  8 CH₃ COOC₂H₅CH₃ CH₃, CH₃ H 574, 612 3.50 7 20  9 CH₃ COOC₂H₅ CH₃ CH₃, CH₃ C(CH₃)₂Ph580, 614 3.50 >20 17 21 (comp.) CH₃ CH₃ CH₃ H H 598 0.30 0.5 1.5 21(comp.) CH₂-(cyclo)C₆H₁₁ (cyclo)C₆H₁₁ H H 610 0.55 0.2 10 21 (comp.)CH₂-(cyclo)C₆H₁₁ (cyclo)C₆H₁₁ H C(CH₃)₂Ph 620 0.70 3 10

1. A photochromic compound selected from a spiro(indoline)naphtho(2,1-b)(1,4)oxazine and a spiro(indoline) naphtho(1,2-b)(1,4)oxazine containinga group selected from: (a) —CH₂—C_(n)F_(2n+1) at the nitrogen atom inthe 1-position on the indoline part of the molecule, wherein n is aninteger of 1 to 6; (b) —COOR at the 3-position on the indoline part ofthe molecule, wherein R is (i) C₁-C₆ alkyl optionally substituted byfluoro, C₁-C₄ alkoxy or fluoroalkoxy, C₁-C₄ alkylcarbonyloxy, C₂-C₄alkenylcarbonyloxy, C₃-C₆ cycloalkyl or aryl; (ii) C₂-C₆ alkenyl with aterminal double bond; (iii) C₃-C₆ cycloalkyl optionally substituted byfluoro; or (iv) aryl; (c) an —OCF₃ group on the benzene ring of theindoline part of the molecule; (d) an aryl(dialkyl)methyl group of theformula —C(aryl)(C_(n)H_(2n+1))(C_(m)H_(2m+1)), wherein n and m areintegers from 1 to 5, linked to one of the benzene rings of thenaphthoxazine part of the molecule; and (e) any combination of (a), (b),(c) and/or (d).
 2. A spiro(indoline)naphtho(2,1-b) (1,4)oxazine or aspiro(indoline) naphtho(1,2-b)(1,4)oxazine according to claim 1,containing a group —CH₂—C_(n)F_(2n+1) at the nitrogen atom in the1-position on the indoline part of the molecule, wherein n is an integerof 1 to
 4. 3. A spiro(indoline)naphtho(2,1-b)(1,4)oxazine orspiro(indoline)naphtho(1,2-b)(1,4) oxazine according to claim 2 havingthe following formulas Ia and Ib, respectively:

wherein (a) n is an integer from 1 to 6; p is 1 or 2; and q is aninteger from 1 to 6; (b) R₂ and R₃ represent independently a radicalselected from: (i) C₁-C₆ alkyl optionally substituted by fluoro, C₁-C₄alkoxy or fluoroalkoxy, C₁-C₄ alkylcarbonyloxy, C₂-C₄alkenylcarbonyloxy, C₃-C₆ cycloalkyl or aryl-; (ii) C₂-C₆ alkenyl with aterminal double bond; (iii) C₃-C₆ cycloalkyl optionally substituted byfluoro; (iv) aryl; (v) alkylcarbonyl; or (vi) one of R₂ and R₃ is agroup —COOR wherein R is a radical (i) to (iv) as defined hereinbeforeand the other of R₂ and R₃ is a radical (i) to (iv) as definedhereinbefore; or (vii) R₂ and R₃ together with the carbon atom atposition 3 of the indoline ring form a 3-7 membered saturated ringoptionally containing a heteroatom selected from nitrogen, oxygen orsulfur, and (c) R₄ and R₅ represent independently (i) hydrogen; (ii)halogen, preferably fluoro; or a radical selected from: (iii) cyano;(iv) aryloxy optionally substituted by C₁-C₆ alkyl, C₁-C₄ alkoxy oramino; (v) C₁-C₄ alkoxy optionally substituted by halogen, preferablydi- and trifluoromethoxy; (vii) C₁-C₆ alkyl optionally substituted byC₁-C₄ alkoxy, halogen, preferably trifluoromethyl, C₃-C₆ cycloalkyl,polycycloalkyl (such as norbomane or adamantane), aryl or heterocyclyl;(viii) aryl optionally substituted with amino or alkoxy group,preferably dialkylaminophenyl or methoxyphenyl; (ix) amide (—CONH₂); (x)sulfonamide (—SO₂NH₂); (xi) —NR₆R₇, wherein R₆ and R₇ are independentlyselected from alkyl, alkenyl, cycloalkyl, aryl, alkylaryl, fluoroalkyl(preferably trifluoromethyl) or R₆ and R₇ together with the nitrogenatom form a 3-7 membered saturated ring optionally containing a furtherheteroatom selected from nitrogen, oxygen or sulfur atom, preferablypiperidino, piperazino or morpholino; (xii) R₄ may further be —OCF₃, inwhich case p is 1; and (xiii) R₅ may further be an aryl(dialkyl)methylgroup of the formula —C(aryl)(C_(n)H_(2n+1))(C_(m)H_(2m+1)), wherein nand m are integers from 1 to 5, linked to one of the benzene rings ofthe naphthoxazine part of the molecule, in which case q is an integerfrom 1 to
 5. 4. A spiro(indoline)naphtho(2,1-b)(1,4)oxazine orspiro(indoline)naphtho(1,2-b)(1,4) oxazine compound according to claim1, containing at the 3-position on the indoline part of the molecule agroup —COOR, wherein R is selected from: (i) C₁-C₆ alkyl optionallysubstituted by fluoro, C₁-C₄ alkoxy or fluoroalkoxy, C₁-C₄alkylcarbonyloxy, C₂-C₄ alkenylcarbonyloxy, C₃-C₆ cycloalkyl or aryl;(ii) C₁-C₆ alkenyl with a terminal double bond; (iii) C₃-C₆ cycloalkyl;or (iv) aryl.
 5. A spiro(indoline)naphtho(2,1-b)(1,4)oxazine orspiro(indoline)naphtho(1,2-b)(1,4) oxazine according to claim 4, havingthe formulas IIa and IIb, respectively:

wherein (a) p is 1 or 2 and q is an integer from 1 to 6; (b) R₁ is aradical selected from: (i) C₁-C₆ alkyl optionally substituted by C₁-C₄alkoxy, C₁-C₄ alkylcarbonyloxy, C₂-C₄ alkenylcarbonyloxy, C₃-C₆cycloalkyl, polycycloalkyl, aryl or heterocyclic ring; (ii) C₃-C₆cycloalkyl; (iii) polycycloalkyl: (iv) aryl; (v) heterocyclic ring; (vi)—CH₂—C_(n)F_(2n+1) wherein n is an integer of 1 to 6; or (vii) C₂-C₆alkenyl with a terminal double bond; (c) R₃ represents a radicalselected from: (i) C₁-C₆ alkyl optionally substituted by fluoro, C₁-C₄alkoxy or fluoroalkoxy, C₁-C₄ alkylcarbonyloxy, C₂-C₄alkenylcarbonyloxy, C₃-C₆ cycloalkyl or aryl; (ii) C₂-C₆ alkenyl with aterminal double bond; (iii) C₃-C₆ cycloalkyl optionally substituted byfluoro ; or (iv) aryl; and (d) R₄ and R₅ represent independently (i)hydrogen; (ii) halogen, preferably fluoro; or a radical selected from:(iii) cyano; (iv) aryloxy optionally substituted by C₁-C₆ alkyl, C₁-C₄alkoxy or amino; (v) C₁-C₄ alkoxy optionally substituted by halogen,preferably di- and trifluoromethoxy; (vii) C₁-C₆ alkyl optionallysubstituted by C₁-C₄ alkoxy, halogen, preferably trifluoromethyl, C₃-C₆cycloalkyl, polycycloalkyl (such as norbomane or adamantane), aryl orheterocyclyl; (viii) aryl optionally substituted with amino or alkoxygroup, preferably dialkylaminophenyl or methoxyphenyl; (ix) amide(—CONH₂); (x) sulfonamide (—SO₂NH₂); (xi) —NR₆R₇, wherein R₆ and R₇ areindependently selected from alkyl, alkenyl, cycloalkyl, aryl, alkylaryl,fluoroalkyl (preferably trifluoromethyl) or R₆ and R₇ together with thenitrogen atom form a 3-7 membered saturated ring optionally containing afurther heteroatom selected from nitrogen, oxygen or sulfur atom,preferably piperidino, piperazino or morpholino; (xii) R₄ may further be—OCF₃, in which case p is 1; and (xiii) R₅ may further be anaryl(dialkyl)methyl group of the formula—C(aryl)(C_(n)H_(2n+1))(C_(m)H_(2m+1)), wherein n and m are integersfrom 1 to 5, linked to one of the benzene rings of the naphthoxazinepart of the molecule, in which case q is an integer from 1 to
 5. 6. Aspiro(indoline)naphtho(2,1-b)(1,4)oxazine andspiro(indoline)naphtho(1,2-b)(1,4) oxazine according to claim 1, havinga trifluoromethoxy (—OCF₃) group on the benzene ring of the indolinepart of the molecule.
 7. A spiro(indoline)naphtho(2,1-b)(1,4)oxazine orspiro(indoline)naphtho(1,2-b)(1,4) oxazine according to claim 6, havingthe formulas IIIa and IIIb, respectively:

(a) q is an integer from 1 to 6; (b) R₁ is a radical selected from: (i)C₁-C₆ alkyl optionally substituted by C₁-C₄ alkoxy, C₁-C₄alkylcarbonyloxy. C₂-C₄ alkenylcarbonyloxy, C₃-C₆ cycloalkyl,polycycloalkyl, aryl or heterocyclic ring; (ii) C₃-C₆ cycloalkyl; (iii)polycycloalkyl: (iv) aryl; (v) heterocyclic ring; (vi)—CH₂-C_(n)F_(2n+1) wherein n is an integer of 1 to 6; or (vii) C₂-C₆alkenyl with a terminal double bond; (c) R₂ and R₃ representindependently a radical selected from: (i) C₁-C₆ alkyl optionallysubstituted by fluoro, C₁-C₄ alkoxy or fluoroalkoxy, C₁-C₄alkylcarbonyloxy, C₂-C₄ alkenylcarbonyloxy, C₃-C₆ cycloalkyl or aryl;(ii) C₂-C₆ alkenyl with a terminal double bond; (iii) C₃-C₆ cycloalkyloptionally substituted by fluoro; (iv) aryl; or (v) alkylcarbonyl; or(vi) one of R₂ and R₃ is a group —COOR wherein R is a radical (i) to(iv) as defined hereinbefore and the other of R₂ and R₃ is a radical (i)to (iv) as defined hereinbefore; or (vii) R₂ and R₃ together with thecarbon atom at position 3 of the indoline ring form a 3-7 memberedsaturated ring optionally containing a heteroatom selected fromnitrogen, oxygen or sulfur, and (d) R₄ and R₅ represent independently(i) hydrogen; (ii) halogen, preferably fluoro; or a radical selectedfrom: (iii) cyano; (iv) aryloxy optionally substituted by C₁-C₆ alkyl,C₁-C₄ alkoxy or amino; (v) C₁-C₄ alkoxy optionally substituted byhalogen, preferably di- and trifluoromethoxy; (vii) C₁-C₆ alkyloptionally substituted by C₁-C₄ alkoxy, halogen, preferablytrifluoromethyl, C₃-C₆ cycloalkyl, polycycloalkyl (such as norbornane oradamantane), aryl or heterocyclyl; (viii) aryl optionally substitutedwith amino or alkoxy group, preferably dialkylaminophenyl ormethoxyphenyl; (ix) amide (—CONH₂); (x) sulfonamide (—SO₂NH₂); (xi)—NR₆R₇, wherein R₆ and R₇ are independently selected from alkyl,alkenyl, cycloalkyl, aryl, alkylaryl, fluoroalkyl (preferablytrifluoromethyl) or R₆ and R₇ together with the nitrogen atom form a 3-7membered saturated ring optionally containing a further heteroatomselected from nitrogen, oxygen or sulfur atom, preferably piperidino,piperazino or morpholino; and (xii) R₅ may further be anaryl(dialkyl)methyl group of the formula—C(aryl)(C_(n)H_(2n+1))(C_(m)H_(2m+1)), wherein n and m are integersfrom 1 to 5, linked to one of the benzene rings of the naphthoxazinepart of the molecule, in which case q is an integer from 1 to
 5. 8. Aspiro(indoline)naphtho(2,1-b)(1,4)oxazine orspiro(indoline)naphtho(1,2-b)(1,4) oxazine according to claim 1, havingan aryl(dialkyl)methyl group of the formula—C(aryl)(C_(n)H_(2n+1))(C_(m)H_(2m+1)), wherein n and m are integersfrom 1 to 5, linked to one of the benzene rings of the naphthoxazinepart of the molecule.
 9. A spiro(indoline)naphtho(2,1-b)(1,4)oxazine orspiro(indoline)naphtho(1,2-b)(1,4) oxazine according to claim 8, havingthe formulas IVa and IVb, respectively:

wherein (a) p is 1 or 2 and q is an integer from 1 to 5; (b) R₁ is aradical selected from: (i) C₁-C₆ alkyl optionally substituted by C₁-C₄alkoxy, C₁-C₄ alkylcarbonyloxy, C₂-C₄ alkenylcarbonyloxy, C₃-C₆cycloalkyl, polycycloalkyl, aryl or heterocyclic ring; (ii) C₃-C₆cycloalkyl; (iii) polycycloalkyl: (iv) aryl; (v) heterocyclic ring; (vi)—CH₂—C_(n)F_(2n+1) wherein n is an integer of 1 to 6; or (vii) C₂-C₆alkenyl with a terminal double bond; (c) R₂ and R₃ representindependently a radical selected from: (i) C₁-C₆ alkyl optionallysubstituted by fluoro, C₁-C₄ alkoxy or fluoroalkoxy, C₁-C₄alkylcarbonyloxy, C₂-C₄ alkenylcarbonyloxy, C₃-C₆ cycloalkyl or aryl;(ii) C₂-C₆ alkenyl with a terminal double bond; (iii) C₃-C₆ cycloalkyloptionally substituted by fluoro; (iv) aryl; or (v) alkylcarbonyl; or(vi) one of R₂ and R₃ is a group —COOR wherein R is a radical (i) to(iv) as defined hereinbefore and the other of R₂ and R₃ is a radical (i)to (iv) as defined hereinbefore; or (vii) R₂ and R₃ together with thecarbon atom at position 3 of the indoline ring form a 3-7 memberedsaturated ring optionally containing a heteroatom selected fromnitrogen, oxygen or sulfur, and (d) R₄ and R₅ represent independently(i) hydrogen; (ii) halogen, preferably fluoro; or a radical selectedfrom: (iii) cyano; (iv) aryloxy optionally substituted by C₁-C₆ alkyl,C₁-C₄ alkoxy or amino; (v) C₁-C₄ alkoxy optionally substituted byhalogen, preferably di- and trifluoromethoxy; (vii) C₁-C₆ alkyloptionally substituted by C₁-C₄ alkoxy, halogen, preferablytrifluoromethyl, C₃-C₆ cycloalkyl, polycycloalkyl (such as norbomane oradamantane), aryl or heterocyclyl; (viii) aryl optionally substitutedwith amino or alkoxy group, preferably dialkylaminophenyl ormethoxyphenyl; (ix) amide (—CONH₂); (x) sulfonamide (—SO₂NH₂); (xi)—NR₆R₇, )wherein R₆ and R₇ are independently selected from alkyl,alkenyl, cycloalkyl, aryl, alkylaryl, fluoroalkyl (preferablytrifluoromethyl) or R₆ and R₇ together with the nitrogen atom form a 3-7membered saturated ring optionally containing a further heteroatomselected from nitrogen, oxygen or sulfur atom, preferably piperidino,piperazino or morpholino; and (xii) R₄ may further be —OCF₃, in whichcase p is
 1. 10. A spiro(indoline)naphtho(2,1-b)(1,4)oxazine orspiro(indoline)naphtho(1,2-b)(1,4) oxazine according to any one ofclaims 1 to 9, wherein any alkyl or alkoxy radical is linear orbranched; any C₂-C₄ alkenylcarbonyloxy radical is preferably the radicalderived from acrylic (—O—CO—CH═CH₂) or methacrylic (—O—CO—(CH₃)═CH₂)acid; any C₃-C₆ cycloalkyl is preferably cyclopentyl or cyclohexyl; thepolycycloalkyl may be a C₄-C₂₀ bicycloalkyl such as partially orcompletely saturated naphthyl or a C₆-C₂₀ tricycloalkyl such asadamantyl and norbornyl; any C₂-C₆ alkenyl with a terminal double bondis preferably —CH₂—CH═CH₂ or —CH₂—(CH₂)₃—CH═CH₂; preferred radicals—CH₂—C_(n)F_(2n+1) are —CH₂—CF₃ and —CH₂—CF₂—CF₃; in the group of theformula —C(aryl)(C_(n)H_(2n+1))(C_(m)H_(2m+1)), n and m are preferably 1such that said linking group is preferably tert-propylene (CH₃)—C—(CH₃).11. A spiro(indoline)naphtho(2,1-b)(1,4)oxazine orspiro(indoline)naphtho(1,2-b)(1,4) oxazine according to any one ofclaims 1 to 10, selected from the compounds:1,3,3-trimethyl-5-trifluoromethoxy-spiro-(indoline-2,3′-(3H)-naphtho[2,1-b]-(1,4)-oxazine)1-Cyclohexylmethyl-3,3-dimethyl-5-trifluoromethoxy-6′-dimethyl-amino-spiro-(indoline-2,3′-(3H)-naphtho[2,1-b]-(1,4)-oxazine)1-Propyl-3,3-dimethyl-5-trifluoromethoxy-6′-dimethylamino-spiro-(indoline-2,3′-(3H)-naphtho[2,1-b]-(1,4)-oxazine)1-Propyl-3,3-dimethyl-5-trifluoromethoxy-6′-piperidino-spiro-(indoline-2,3′-(3H)-naphtho-[2,1-b]-(1,4)-oxazine)1,3-Dimethyl-3-carboethoxy-spiro-(indoline-2,3′-(3H)-naphtho[2,1-b]-(1,4)-oxazine)1-Cyclohexylmethyl-3-methyl-3-carboethoxy-spiro-(indoline-2,3′-(3H)-naphtho[2,1-b]-(1,4)-oxazine1,3,4,5-Tetramethyl-3-carboethoxy-spiro-(indoline-2,3′-(3H)-naphtho-[2,1-b]-(1,4)-oxazine)1,3,4,5-Tetramethyl-3-carboethoxy-8′-(1-methyl-1-phenyl)ethyl-spiro-(indoline-2,3′-(3H)-naphtho[2,1-b]-(1,4)-oxazine)1,3-Dimethyl-3-carboethoxy-9′-acetyloxy-spiro-(indoline-2,3′-(3H)-naphtho-[2,1-b]-(1,4)-oxazine)1-Isobutyl-3-methyl-3-carboethoxy-spiro-(indoline-2,3′-(3H)-naphtho-[2,1-b]-(1,4)-oxazine)1-Isobutyl-3,5-dimethyl-3-carboethoxy-spiro-(indoline-2,3′-(3H)-naphtho-[2,1-b]-(1,4)-oxazine)1,3-Dimethyl-3-carboethoxy-8′-(1-methyl-1-phenyl)-ethyl-spiro-(indoline-2,3′-(3H)-naphtho-[2,1-b]-(1,4)-oxazine)1,3,5,6-Tetramethyl-3-carboethoxy-spiro-(indoline-2,3′-(3H)-naphtho-[2,1-b]-(1,4)-oxazine)1-Cyclohexylmethyl-3-methyl-3-carboethoxy-6′-dimethylamino-spiro-(indoline-2,3′-(3H)-naphtho-[2,1-b]-(1,4)-oxazine)1-Propyl-3,5-Dimethyl-3-carboethoxy-spiro-(indoline-2,3′-(3H)-naphtho-[2,1-b]-(1,4)-oxazine)1,3-Dimethyl-3-carboethoxy-6′-methoxy-spiro-(indoline-2,3′-(3H)-naphtho-[2,1-b]-(1,4)-oxazine)1-(2-Phenylethyl)-3-methyl-3-carboethoxy-spiro-(indoline-2,3′-(3H)-naphtho-[2,1-b]-(1,4)-oxazine)1-Ethyl-3,5-dimethyl-3-carboethoxy-spiro-(indoline-2,3′-(3H)-naphtho-[2,1-b]-(1,4)-oxazine)1-Isobutyl-5-fluoro-3-methyl-3-carboethoxy-spiro-(indoline-2,3′-(3H)-naphtho-[2,1-b]-(1,4)-oxazine)1-(2,2,2-trifluoroethyl)-3,3-dimethyl-6′(4-diethylaminophenyl)-spiro-(indoline-2,3′-(3H)-naphtho-[2,1-b]-(1,4)-oxazine)1-(2,2,2-Trifluoroethyl)-3,3-dimethyl-spiro-(indoline-2,3′-(3H)-naphtho-[2,1-b]-(1,4)-oxazine)1-Cyclohexylmethyl-3,3-spiro-(cyclohexyl)-8′-(1-methyl-1-phenyl)ethyl-spiro-(indoline-2,3′-(3H)-naphtho-[2,1-b]-(1,4)-oxazine)1-Cyclohexylmethyl-3,3-dimethyl-8′-(1-methyl-1-phenyl)ethyl-spiro-(indoline-2,3′-(3H)-naphtho-[2,1-b]-(1,4)-oxazine)1-Cyclohexylmethyl-3,3-dimethyl-6′-morpholino-8′-(1-methyl-1-phenyl)ethyl-spiro-(indoline-2,3′-(3H)-naphtho-[2,1-b]-(1,4)-oxazine)1-Cyclohexylmethyl-3,3-dimethyl-6′-morpholino-8′-(1-methyl-1-phenyl)ethyl-spiro-(indoline-2,3′-(3H)-naphtho-[1,2-b]-(1,4)-oxazine)1-Propyl-3,5-Dimethyl-3-carboethoxy-spiro-(indoline-2,3′-(3H)-naphtho-[1,2-b]-(1,4)-oxazine)12. A plastic organic photochromic article comprising a plastic hostmaterial containing a photochromic compound as claimed in any one ofclaims 1 to 11, or a mixture thereof.
 13. A photochromic articleaccording to claim 12 containing one or more compounds according to anyone of claims 1 to 11 and another photochrome known in the art.
 14. Aphotochromic article according to claim 12 or 13 further containingplasticizers, light stabilizers and/or materials for the photochromemicroencapsulation.
 15. A photochromic article according to any one ofclaims 12 to 14, said article being a plastic lens.